Diastereo- and Enantioselective Synthesis of Organometallic Bis(helicene)s by a Combination of C-H Activation and Dynamic Isomerization

作者：Shen Chengshuo; Anger Emmanuel; Srebro Monika; Vanthuyne Nicolas; Toupet Loic; Roussel Christian; Autschbach Jochen^*; Reau Regis; Crassous Jeanne

来源：Chemistry - A European Journal, 2013, 19(49): 16722-16728.

DOI：10.1002/chem.201302479

• CH activation
• chiroptical properties
• density functional calculations
• helicenes
• isomerization

Homochiral and heterochiral cis-bis-cycloplatinated-[6]helicene derivatives 1b(1,2), as representative examples of platina[6]helicenes that share a common platinum center, have been prepared. A diastereo- and enantioselective synthesis, which combines CH activation and dynamic isomerization from heterochiral structure 1b(2) into homochiral structure 1b(1), is also described. Overall, this isomerization process results in the transfer of chiral information from one helicene moiety to the other one. The chiroptical properties of homochiral (P)- and (M)-1b(1) were greatly modified upon oxidation into their corresponding (P)- and (M)-diiodo-Pt-IV complexes (5). The changes were also analyzed by performing theoretical calculations. CH activation in the synthesis of organometallic helicenes is further demonstrated by the preparation of cis-bis-cycloplatinated-[8]helicene 1c.

• 出版日期2013-12-2